JP3270704B2 - Method for manufacturing semiconductor microstructure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor thin film for realizing an electronic functional device or an optical functional device, and more particularly, to a semiconductor device having a facet surface perpendicular to a main surface of a substrate. And a method for manufacturing a sub-micrometer scale microstructure.

[0002]

2. Description of the Related Art In order to realize more advanced electronic functional devices and optical functional devices, further improvement in semiconductor crystal fabrication and processing techniques is required. For example, considering a semiconductor laser that is an optical functional element, it is necessary to fabricate a semiconductor flat surface completely perpendicular to the substrate in order to effectively induce stimulated emission of light. Conventional techniques for this purpose include cleavage and wet etching (Literature: SL McCall, A.
FJ Levi, RE Slusher, SJ Pearton and RA
Logan, Appl. Phys. Lett. 60, 289 (1992)) and dry etching (Literature: A. Behfar-Red, SS Wong,
JM Ballantyne, BA Soltz and CM Harding, A
ppl. Phys. Lett. 54, 493 (1989)) or selective growth using a mask (literature: T. Fukui and S. Ando, Appl.
Phys. Lett. 58, 2018 (1991)) has been used.

[0003]

Conventionally, a flat surface of a semiconductor completely perpendicular to a substrate has been manufactured as described above. However, the following problems are limited to nitride semiconductors only. there were.

First, nitride semiconductors have poor cleavage properties, and a flat cleavage plane at the atomic level cannot be obtained. In addition, the cleavage method can be processed only on a large scale of about 100 μm. Furthermore, since nitride semiconductors are generally very hard and chemically inert, it has been difficult to process a flat surface perpendicular to the substrate surface by a physical or chemical etching technique.

The present invention has been made to solve the above-mentioned problems, and is intended to be perpendicular to a substrate surface.
It is an object of the present invention to provide a method for forming a micrometer-scale minute hexagonal prism structure of a nitride semiconductor having a flat facet surface at an atomic level.

[0006]

An outline of a method for manufacturing a semiconductor microstructure according to the present invention will be described below.

First, a sapphire substrate whose main surface is a (001) plane is heated, and a gas containing a nitrogen compound and a gas containing a compound of a group III element are introduced into the main surface. A first nitride semiconductor thin film having an amorphous structure is formed on the main surface and heated in an atmosphere of a gas containing a nitrogen compound, whereby a single crystal nitride semiconductor thin film is formed by solid phase epitaxial growth.

Then, a gas containing a nitrogen compound and a gas containing a compound of a group III element are introduced into the surface of the heated single-crystal nitride semiconductor thin film to form a relatively thick second nitride semiconductor. The thin film is grown by vapor phase epitaxial growth.

Further, a silicon dioxide thin film is formed on the second nitride semiconductor thin film by photolithography, the aperture ratio is 50% or more, and the shortest distance between adjacent windows is 100 μm or less. Then, a mask having a window exposing the surface of the second nitride semiconductor thin film is formed.

Finally, the substrate after the formation of the mask is heated, and a gas containing a nitrogen compound and a gas containing a compound of a group III element are introduced, whereby the microstructure of the nitride semiconductor is brought into contact with the window. Is vapor-phase-selective-epitaxially grown. The nitride semiconductor microstructure grown in this manner becomes a hexagonal prism structure surrounded by a {1-100} plane, which is a flat facet plane perpendicular to the substrate surface. In the notation of the Miller index representing the surface, the minus sign is displayed not to the upper part of the numeral but to the left of the numeral. In this application, this notation is used except in the drawings.

If the window includes at least one pair of parallel straight sides and the side is parallel to the [1-100] direction of the sapphire substrate, the facet is Since the edge is formed starting from the side, the position of the facet can be accurately determined.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a configuration diagram showing a basic configuration of a semiconductor thin film manufacturing apparatus used in the present invention. In the figure, 1 is a reaction tank, 2 is a substrate support, 3 is a heater for heating the substrate, 4 is a sapphire substrate whose main surface is a (001) plane, and 5 is a semiconductor thin film to be grown. This is a supply pipe for supplying gas as a raw material.

First, a sapphire substrate 4 is placed on a substrate support 2 in a reaction tank 1, the pressure is maintained at about 76 Torr while flowing an inert gas and hydrogen through a supply pipe 5 for several slm, and the substrate 4 is kept at 1000 ° C. Heat to about. Where slm is
It is an abbreviation of standard liter per minute, and is a unit of volume velocity (liter / minute) when the amount of gas is represented by a volume in a standard state (0 ° C., 1 atm). This state is about 1
The process is continued for 0 minute, and the surface of the sapphire substrate 4 is thermally cleaned. Next, ammonia gas was added to the reactor 1 for 0.2
Introduce about 5 slm and wait for about 1 minute. In this process, the surface of the sapphire substrate 4 is nitrided, and a thin layer (a few atomic layers) of aluminum nitride having small lattice mismatch with the gallium nitride thin film is formed. Next, the temperature of the substrate 4 is set to about 600
The temperature was lowered to about 5 ° C., and trimethylgallium was introduced from the supply pipe 5 at a rate of about 6 μmol / min to deposit a gallium nitride thin film having an amorphous structure to a thickness of about 40 nm.

The supply of trimethylgallium is stopped and the substrate 4
When the temperature is raised again to about 1000 ° C., the above-mentioned gallium nitride thin film having the amorphous structure undergoes solid phase epitaxial growth, and becomes a single crystal structure. Further, trimethylgallium is introduced again at a rate of about 6 micromol / min, and vapor phase epitaxial growth is performed to form a 1500-nm-thick single-crystal gallium nitride thin film. The crystal orientation relationship between the single crystal gallium nitride thin film and the sapphire substrate was as shown in FIG.

The <001> direction of sapphire is parallel to the <001> direction of gallium nitride, and [1 1 -2]
The [0] direction is parallel to the [1-100] direction of gallium nitride, and the [1-100] direction of sapphire is [11-2] of gallium nitride.
0] direction.

That is, when the gallium nitride thin film has a c-axis <0 0
It was found that by rotating by 30 degrees around the <1> axis, the lattice mismatch between the sapphire substrate and the gallium nitride thin film became smaller, and a high-quality single-crystal gallium nitride thin film was grown. In FIG. 2, gallium nitride is G
aN.

A silicon dioxide thin film having a thickness of about 50 nm is formed on the surface of the single crystal gallium nitride thin film having a thickness of 1500 nm by sputtering. Next, a circular, hexagonal, or rectangular fine window pattern is formed on the silicon dioxide by photolithography to partially expose the surface of the single crystal gallium nitride thin film. In this embodiment, the opening ratio of the window (the ratio of the total area of the window where the gallium nitride thin film is exposed to the total area of the main surface of the substrate) is 75%.
And FIG. 3 shows an example of each pattern. In FIG.
The gray part indicates the window part, and the arrow indicates the orientation of the sapphire substrate. In this case, a rectangular pattern (FIG. 3)
(A)) in the longitudinal direction and the hexagonal pattern (FIG. 3)
It is important that each side of (b)) is parallel to the [1-100] direction of the sapphire substrate (the [11-20] direction of the gallium nitride thin film).

This is again inserted into the reaction tank 1 and placed on the substrate support 2, and the pressure is maintained at about 76 Torr by flowing an inert gas and hydrogen several slm through the supply pipe 5. Next, the temperature is raised to about 1000 ° C., and ammonia gas is introduced into the reaction vessel 1 through the supply pipe 5 at a rate of 0.25 slm and trimethylgallium at a rate of about 6 μmol / min. Then
Gallium nitride is selectively epitaxially grown only in the opening where the single crystal gallium nitride thin film is exposed without the silicon dioxide mask, and no gallium nitride is deposited on the silicon dioxide thin film. As a result, a small nitride semiconductor hexagonal column structure with a scale of several μm or less surrounded by a flat vertical facet surface is formed.

FIG. 4 shows a photograph (FIG. 4A) of a hexagonal prism grown on a circular window pattern having a diameter of 5 μm through the above-mentioned steps by a scanning electron microscope (FIG. 4A) and a schematic diagram of a cross section (FIG. 4).
(B)) is shown. In FIG. 4B, gallium nitride and silicon dioxide are GaN and SiO2, respectively.
2 is represented. In FIG. 4B, the edges of the hexagonal prism are also displayed. As shown in FIG. 4A, the length of the diagonal passing through the center point is slightly more than 5 μm and the height is 8 μm.
It can be seen that a very tall hexagonal column m is formed. The sides of this hexagonal prism are equivalent six {1-100} planes, which are completely perpendicular to the substrate surface. In addition, the upper end face ((0 0 1 1) face) and side face (｛1 -10
0 ° plane) is extremely flat. Since this hexagonal prism has a high light confinement effect, it can be applied to a ring resonator laser that can oscillate at a low threshold.

The hexagonal column shown in FIG. 4 grows overgrowth slightly out of the circular pattern. By changing the flow rate ratio between the source gas, ammonia and trimethylgallium, the size of this overgrowth can be adjusted while keeping the height of the hexagonal prism constant. For this reason, as shown in FIG. 5, a hexagonal column of a nitride semiconductor that protrudes largely on a silicon oxide mask can also be manufactured. FIG. 5 is a schematic cross-sectional view. As in FIG. 4B, gallium nitride and silicon dioxide are represented by GaN and SiO2, respectively.
In addition, the ridge of the hexagonal column is also displayed. The protruding portion (the hatched portion in FIG. 5) is less affected by a sapphire substrate having a different lattice constant, and thus has few lattice defects. Therefore, this portion has better optical and electrical characteristics than the nitride semiconductor formed directly on the sapphire substrate.

FIG. 6 shows that the length of the diagonal line passing through the center is 16 μm.
1 shows a scanning electron micrograph of a gallium nitride hexagonal column grown on a m hexagonal window pattern. One side of the hexagonal window pattern is parallel to the [1-100] direction of the sapphire substrate (the [11-20] direction of the gallium nitride thin film). in this way,
Even in a hexagonal prism with a long diagonal line passing through the center point,
An extremely flat top surface (upper surface) is obtained. When gallium nitride is selectively grown directly on a sapphire substrate, which is a foreign substance, the periphery of the mask pattern rises and the center is dented, that is, so-called ridge growth occurs, and a structure having a shape that is difficult to apply to devices is formed. In the present invention, since the selective growth is performed on gallium nitride, uniform and two-dimensional crystal growth is promoted, and even if the length of the diagonal line passing through the center point is large, a hexagonal prism structure having a flat top surface was gotten. This is a feature that is advantageous for application to laser diodes and transistors that require a double heterostructure or a superlattice structure.

When a window pattern having a rectangular shape is used, a hexagonal column having a hexagonal bottom surface having two long sides parallel to the long side of the rectangle as shown in FIG. 7 is formed.
7A is a plan view and FIG. 7B is a cross-sectional view. In this case, as in FIGS. 4B and 5, gallium nitride and silicon dioxide are
It is expressed by GaN and SiO2, and the ridge of a hexagonal prism is also shown. In order to obtain a flat vertical facet, the long side of the rectangular mask must be [1 -1
It is important that they are parallel to the [0 0] direction (the [1 1 -2 0] direction of the gallium nitride thin film).

The mechanism by which the hexagonal prism is formed by the manufacturing method of the present invention is as follows. The raw material is effectively decomposed on the surface of the gallium nitride exposed at the opening, and is diffused in the lateral direction to form a hexagonal prism. It is presumed that by reaching the window, the raw materials necessary for forming the hexagonal prism are sufficiently supplied. Therefore, if the distance between the adjacent windows is too large, the raw material decomposed on the gallium nitride surface exposed to the adjacent windows diffuses into the gas phase before reaching the windows forming the hexagonal columns. As a result, it is not effectively supplied to the window forming the hexagonal prism. As a result of studying the case of various intervals, the interval between the window forming the hexagonal prism and the adjacent window was 10
When the thickness is 0 μm or less, a hexagonal prism having vertical facets can be grown, and it has been confirmed that the effects of the present invention can be effectively obtained. In addition, there is an optimum range of the aperture ratio in relation to the mechanism. For example, aperture ratio 2
In the experimental results for the case of 5%, hexagonal prisms having vertical facets could not be grown because all the above-mentioned ridge growth occurred remarkably. Therefore, as a result of examining the aperture ratio in various cases, it was confirmed that when the aperture ratio was 50% or more, a hexagonal prism having vertical facets could be grown, and the effect of the present invention could be effectively obtained. did. As a window for maintaining a large aperture ratio, a necessary number of windows for forming a hexagonal prism may be provided, but a large area is provided at a portion separated from the hexagonal prism by the necessary distance described above. A window may be provided.

[0024]

As described above, according to the present invention, it is possible to manufacture a nitride semiconductor hexagonal column structure having a scale of about several μm to about several tens of μm surrounded by a flat vertical facet surface. Become. Therefore, it is possible to manufacture a high-performance micro facet laser using a nitride semiconductor.

[Brief description of the drawings]

FIG. 1 is a schematic view of a reaction tank used in an example of the present invention.

FIG. 2 is a diagram showing a relationship between crystal orientations of a sapphire substrate and a gallium nitride thin film.

FIG. 3 is a view showing a window pattern for selectively growing a gallium nitride microstructure.

FIG. 4 is a scanning electron micrograph and a schematic diagram of a hexagonal column of gallium nitride produced by selective growth.

FIG. 5 is a schematic view of a gallium nitride hexagonal column overgrown on a silicon dioxide mask.

FIG. 6 is a scanning electron micrograph of a gallium nitride hexagonal column grown on a hexagonal window pattern having a diagonal length of 16 μm passing through the center.

FIG. 7 is a schematic diagram of a gallium nitride hexagonal column formed using a rectangular window pattern.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Reaction tank, 2 ... Substrate support, 3 ... Heater for heating a substrate, 4 ... Sapphire substrate, 5 ... Source gas supply pipe.

Continuation of the front page (72) Inventor Naoki Kobayashi 3-19-2 Nishi Shinjuku, Shinjuku-ku, Tokyo Within Nippon Telegraph and Telephone Corporation (56) References JP-A-8-64791 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) H01L 21/20 H01L 21/205

Claims (2)

(57) [Claims] 1. A sapphire substrate whose main surface is a (001) plane is heated, and a gas containing a nitrogen compound and a gas containing a compound of a group III element are introduced onto the main surface. A first step of forming a first nitride semiconductor thin film having an amorphous structure on the main surface; and heating the first nitride semiconductor thin film in an atmosphere of a gas containing a nitrogen compound, A second step of single crystallization by solid phase epitaxial growth, and introducing a gas containing a nitrogen compound and a gas containing a compound of a group III element to the surface of the heated first nitride semiconductor thin film. A third step of vapor-phase epitaxially growing a second nitride semiconductor thin film; and a window formed of a silicon dioxide thin film on the surface of the second nitride semiconductor thin film, having an aperture ratio of 50% or more, and an adjacent window. The shortest distance to is 100 a fourth step of forming a mask having a plurality of windows exposing the second nitride semiconductor thin film having a thickness of not more than μm, and adding nitrogen to a portion of the window where the heated second nitride semiconductor thin film is exposed. A fifth step of introducing a gas containing a compound and a gas containing a compound of a Group III element to vapor-phase selective epitaxial growth of the nitride semiconductor microstructure on the window portion by introducing a gas. A method for manufacturing a semiconductor microstructure, which is characterized by the following. 2. The method according to claim 1, wherein the window includes at least one pair of parallel straight sides, and the parallel sides are parallel to a [100] direction of the sapphire substrate. Item 2. The method for manufacturing a semiconductor microstructure according to Item 1.